EP2091984B1 - Agents mouillants et agents dispersants à base de mélanges de copolymères structurés - Google Patents

Agents mouillants et agents dispersants à base de mélanges de copolymères structurés Download PDF

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Publication number
EP2091984B1
EP2091984B1 EP07818854.7A EP07818854A EP2091984B1 EP 2091984 B1 EP2091984 B1 EP 2091984B1 EP 07818854 A EP07818854 A EP 07818854A EP 2091984 B1 EP2091984 B1 EP 2091984B1
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EP
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Prior art keywords
copolymers
composition according
polymer
meth
pigments
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German (de)
English (en)
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EP2091984A2 (fr
Inventor
Bernd Göbelt
Jürgen OMEIS
Sabine Stelz
Sandra KÖHLER
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BYK Chemie GmbH
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BYK Chemie GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the invention relates to the mixtures of two linear, structured copolymers, which are characterized by the choice of two different polymerization techniques and different molecular weight distributions (polydispersities) M w / M n , and are suitable as dispersants, for the treatment of pigments and as an additive in coating compositions and molding compositions. Furthermore, the invention relates to the use of such mixtures as wetting and dispersing agents.
  • RAFT Reversible Addition Fragmentation Chain Transfer Process
  • MADIX MADIX
  • Additional Fragmentation Chain Transfer when using certain polymerization.
  • RAFT is for example in Polym. Int. 2000, 49, 993 . Aust. J. Chem 2005, 58, 379 . J. Polym. Sci. Part A: Polym. Chem. 2005, 43, 5347 . US 6,291,620 .
  • WO 98/58974 and WO 99/31144 described.
  • NMP polymerization regulators
  • ARP Atom Transfer Radical Polymerization
  • GTP Group Transfer Polymerization
  • GTP Group Transfer Polymerization
  • block copolymers and gradient copolymers are referred to as structured copolymers.
  • mixtures of two linear, structured copolymers which are characterized in that they are prepared by two different controlled polymerization techniques and have different molecular weight distributions (M w / M n ), with the same pigment dispersion, inks or liquid stabilized pigment dispersion Coating agents and appropriate viscosity reduction have a broader compatibility with different binder systems, as the wetting and dispersing agents of the prior art.
  • Mixtures or compositions according to the invention are understood as meaning those which comprise at least two structured linear copolymers which are selected from the group consisting of block copolymers and gradient copolymers and these copolymers are prepared by different controlled polymerization techniques and the difference in the polydispersities of these copolymers ⁇ (M w / M n ) ⁇ 0.25.
  • the mixtures may contain two copolymers which differ in their polymer structures, molecular weights and monomer compositions.
  • Structured copolymers of the mixtures according to the invention are gradient copolymers and linear block copolymers.
  • Gradient copolymers of the blends of the invention are linear copolymers in which the concentration of an ethylenically unsaturated monomer or mixture of ethylenically unsaturated monomers continuously decreases along the polymer chains from their beginning to their end and the concentration of another ethylenically saturated monomer or other mixture of ethylenically unsaturated Monomers increases.
  • Such gradient copolymers are, for example, in EP 1 416 019 and in WO 01/44389 described.
  • both structured linear copolymers of the composition according to the invention can also be gradient copolymers.
  • Block copolymers of the polymer blends according to the invention are linear copolymers which are obtained by adding at least two different ethylenically unsaturated monomers, two different mixtures of ethylenically unsaturated monomers or by adding an ethylenically unsaturated monomer and a mixture of ethylenically unsaturated monomers at different times when carrying out a controlled polymerization, wherein an ethylenically unsaturated monomer or a mixture of ethylenically unsaturated monomers at the beginning of the reaction can be submitted in the reaction vessel.
  • block copolymers When adding the further ethylenically unsaturated monomer or the mixture of ethylenically unsaturated monomers or the addition of ethylenically unsaturated monomers with several additions, the ethylenically unsaturated monomers that are in the reaction vessel, have already completely reacted, but also partially present.
  • block copolymers contain at least one erratic transition in their composition of ethylenically saturated monomers along the polymer chain, which represents the boundary between the individual blocks.
  • Such block copolymer structures are, for example, AB diblock copolymers, ABA or ABC triblock copolymers as may be used in the present invention.
  • Block copolymers as used in the present invention contain blocks having a minimum of 3 copolymerized ethylenically unsaturated monomers per block.
  • both structured linear copolymers of the composition according to the invention are block copolymers, these being preferably selected from the group consisting of AB, ABA and ABC block copolymers.
  • one of the two copolymers is a gradient copolymer and the other is a block copolymer. If block copolymers are used alone or with gradient copolymers, preferably at least one block copolymer has an AB structure.
  • block copolymers in which at least one of the blocks is composed of at least two different copolymerized ethylenically unsaturated monomers.
  • all blocks within the block copolymer each contain at least two different copolymerized ethylenically unsaturated monomers.
  • the blocks each contain at least three, four or five different copolymerized monomers.
  • the individual polymers of the mixture according to the invention preferably have a number average molecular weight M n of from 1000 to 20 000 g / mol, more preferably from 2000 to 20 000 g / mol and very particularly preferably from 2000 to 15000 g / mol.
  • the individual polymers in the copolymer mixture according to the invention are distinguished by a different molecular weight distribution M w / M n , which preferably ranges from 1.05 to 4.0.
  • the difference in the molecular weight distribution (polydispersity) ⁇ (M w / M n ) between the individual copolymers is at least 0.25.
  • the structured copolymers of the polymer mixtures according to the invention preferably contain polar ethylenically unsaturated monomers from the group of ethylenically unsaturated monomers containing amino groups and / or the ethylenically unsaturated monomers containing acid groups and the reaction products of the amino groups or acid groups to form salts.
  • Amino group-containing ethylenically unsaturated monomers wherein the notation of (meth) acrylate includes both acrylates and methacrylates, for example: aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate ; Aminoalkyl (meth) acryamides such as N, N-dimethylaminopropyl (meth) acrylamide or basic vinyl heterocycles such as 4-vinylpyridine and vinylimidazole.
  • aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate
  • Aminoalkyl (meth) acryamides such as N, N-dimethylaminopropyl (meth
  • Amino group-containing ethylenically unsaturated monomers can also be produced by polymer-analogous reactions after the formation of the polymer chain.
  • oxirane-containing ethylenically unsaturated monomers such as glycidyl methacrylate can be reacted with amines after the polymerization.
  • Reaction products of amino group-containing, ethylenically unsaturated monomers to salts for example, by salification of polymer-bound amino groups with carboxylic acids, sulfonic acids or phosphoric acids and their esters are obtained, as described for example in US 6111054 is described.
  • amino groups in alkylation reactions for example, with benzyl chloride or a combination of oxirane with carboxylic acids to salify quaternary ammonium groups.
  • Tertiary amines can be converted with oxygen, peroxo compounds such as percarboxylic acids and with hydrogen peroxide into amine oxides, which can be additionally salified with acids such as hydrochloric acid.
  • Acid group-containing ethylenically unsaturated monomers include: carboxylic acid group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and 4-vinylbenzoic acid; sulfonic acid group-containing ethylenically unsaturated monomers such as 4-vinylbenzenesulfonic acid, 2-methyl-2- (1-oxo-2-propenyl) amino] -1-propanesulfonic acid, 3- (methacryloyloxy) -propanesulfonic acid and 3- (acryloyloxy) -propanesulfonic acid; phosphorus acidic ethylenically unsaturated monomers such as tripropylene glycol (meth) acrylate phosphate, vinylphosphonic acid and vinylidene diphosphonic acid.
  • carboxylic acid group-containing ethylenically unsaturated monomers such as acrylic acid, methacryl
  • Acid group-containing ethylenically unsaturated monomers can also be produced by polymer-analogous reactions after the construction of the polymer chain. Salts of acid group-containing ethylenically unsaturated monomers can be obtained, for example, by reaction with bases.
  • Suitable bases include, for example, amines such as dimethylaminoethanol, diethanolamine, triethanolamine, 2- (dimethylamino) propan-1-ol, triethylamine, butylamine and dibutylamine; Hydroxides, oxides, carbonates and bicarbonates of metals of the 1st to 3rd main group of the Periodic Table of the Elements, such as sodium hydroxide, potassium hydroxide, aluminum hydroxide and sodium bicarbonate; and heterocyclic nitrogen compounds such as imidazole.
  • amines such as dimethylaminoethanol, diethanolamine, triethanolamine, 2- (dimethylamino) propan-1-ol, triethylamine, butylamine and dibutylamine
  • Hydroxides, oxides, carbonates and bicarbonates of metals of the 1st to 3rd main group of the Periodic Table of the Elements such as sodium hydroxide, potassium hydroxide, aluminum hydroxide and sodium bicarbonate
  • Hydroxy groups in the ethylenically unsaturated monomers can be reacted, for example, with polyphosphoric acid to phosphoric acid esters.
  • polyphosphoric acid to phosphoric acid esters.
  • oxirane structures in ethylenically unsaturated monomers and orthophosphoric acid can be reacted, for example, with polyphosphoric acid to phosphoric acid esters.
  • carboxylic acid functions can be formed from ester-containing, ethylenically unsaturated monomers.
  • the ester such as an alkyl (meth) acrylate acid catalytically to the carboxylic acid function or when using bases by saponification to its corresponding salt can be implemented.
  • reaction products of acid group-containing, ethylenically unsaturated monomers can be used to form salts in the polymerization.
  • reaction products which are used directly as monomers in the polymerization are mentioned above, but may, for example, also be sodium (meth) acrylate, sodium tripropylene glycol (meth) acrylate phosphate, potassium (3-sulfopropyl) (meth) acrylate, sodium 3 allyloxy-2-hydroxypropanesulfonic acid and dipotassium bis (3-sulfopropyl) itaconic acid diester.
  • alkyl (meth) acrylates of straight-chain, branched or cycloaliphatic alcohols having 1 to 22 carbon atoms such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and t- butyl (meth) acrylate;
  • Aryl (meth) acrylates such as benzyl methacrylate or phenyl acrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four
  • the above-mentioned ethylenically unsaturated monomers in the polymers can also be subsequently changed in polymer-analogous reactions.
  • oxirane structures in the polymer can be reacted with nucleophiles such as 4-nitrobenzoic acid.
  • Hydroxy functionalities of the incorporated in the polymer ethylenically unsaturated monomers can be reacted with lactones such as ⁇ -caprolactone to polyesters.
  • lactones such as ⁇ -caprolactone
  • alcohol functions can be formed from these ester functions by acid- or base-catalyzed ester cleavage.
  • the monofunctional initiators used for the preparation of the copolymers of the invention start a polymer chain with only one growth direction.
  • the monofunctional initiators used in the particular controlled, controlled polymerization process are known to one of ordinary skill in the art.
  • initiators for example, azo initiators such as azobisisobutyronitrile, peroxide compounds such as dibenzoyl peroxide and dicumyl peroxide and also persulfates such as ammonium, sodium and potassium peroxodisulfate can be used.
  • polymerization techniques for the preparation of the copolymers to be used in the compositions according to the invention are all known from the prior art living controlled polymerization techniques such as RAFT, MADIX, NMP, ATRP, GTP, the controlled free radical polymerization with tetraphenylethane, the controlled radical polymerization with 1,1- Diphenylethen, the controlled free radical polymerization with inifertem and the controlled radical polymerization with organocobalt complexes.
  • NMP adducts of the initiator with the polymerization regulator can be used in the NMP, such as in Chem. Rev. 2001, 101, 3661, V. Approaches to alkoxyamines " or in Angewandte Chemie Int. Ed. 2004, 43, 6186 described.
  • the polymerization can be carried out solvent-free in substance or in organic solvents and / or water. If solvents are used, the polymerization can be carried out as a conventional solvent polymerization in which the polymer is dissolved in the solvent, or as emulsion or miniemulsion polymerization, as described, for example, in US Pat Angewandte Chemie Int. Ed. 2004, 43, 6186 and Macromolecules 2004, 37, 4453 will be performed.
  • the resulting emulsion or miniemulsion polymer can be made water-soluble by salt formation, so that a homogeneous polymer solution is formed. However, the polymers may still be water insoluble after salification.
  • the copolymers obtained are not necessarily defined as the end group via the polymerization regulator.
  • the end group can, for example be split off completely or partially after the polymerization.
  • This elimination of the polymerization regulator can also be effected, for example, by addition of further chemical compounds, such as polymerization inhibitors, for example phenol derivatives, or by a process as described in US Pat Macromolecules 2001, 34, 3856 is described happen.
  • the RAFT regulator can be thermally cleaved from the polymer by increasing the temperature, removed from the polymer by addition of oxidants such as hydrogen peroxide, peracids, ozone, or other bleaching agents, or reacted with nucleophiles such as amines to form a thiol end group.
  • oxidants such as hydrogen peroxide, peracids, ozone, or other bleaching agents, or reacted with nucleophiles such as amines to form a thiol end group.
  • halogen end groups generated by ATRP can be eliminated by elimination reactions or converted by substitution reactions into other end groups. Examples of such transformations are in Chem. Rev. 2001, 101, 2921 listed.
  • the copolymers thus obtained are reacted in a mixing operation, which can be assisted by heating the polymer solutions, to the polymer mixture according to the invention. If two copolymers are used, the weight ratio of the two copolymers is preferably between 5:95 and 95: 5, more preferably between 10:90 and 90:10 and most preferably between 20:80 and 80:20.
  • compositions according to the invention preferably comprise at most 10% by weight, more preferably at most 5% by weight and most preferably at most 1% by weight of one or more random copolymers or homopolymers formed by termination reactions during the polymerization.
  • the compositions according to the invention are free or essentially free of random copolymers and homopolymers.
  • copolymer mixtures according to the invention can be carried out according to the prior art for known dispersants, wherein instead of the dispersants known in the art those according to the invention are used. So these z. B. in the manufacture or processing of paints, printing inks, inks for inkjet printing, paper coating, leather and textile dyes, pastes, pigment concentrates, ceramics, cosmetic preparations are used, especially if they contain solids such as pigments and / or fillers.
  • compositions based on synthetic, semi-synthetic or natural macromolecular substances such as polyvinyl chloride, saturated or unsaturated polyesters, polyurethanes, polystyrenes, polyacrylates, polyamides, epoxy resins, polyolefins such as polyethylene or polypropylene they are used.
  • binder and / or Solvents, pigments and optionally fillers, the copolymer blends and conventional excipients are mixed use.
  • conventional binders are resins based on polyurethanes, cellulose nitrates, cellulose acetobutyrates, alkyds, melamines, polyesters, chlorinated rubbers, epoxides and (meth) acrylates.
  • water-based coatings examples include cathodic or anodic electrodeposition coatings, for example for automobile bodies. Further examples are plasters, silicate paints, emulsion paints, water-based paints based on water-dilutable alkyds, alkyd emulsions, hybrid systems, 2-component systems, polyurethane and acrylate dispersions.
  • the copolymer mixtures according to the invention are also particularly suitable for the production of solid concentrates, such as, for example, pigment concentrates.
  • the novel copolymer mixtures are initially introduced in a carrier medium, such as organic solvents, plasticizers and / or water, and the solids to be dispersed are added with stirring. Additionally, these concentrates may contain binders and / or other adjuvants. With the However, according to the invention copolymer mixtures, it is particularly possible to produce stable binder-free pigment concentrates.
  • the press cake which may still contain organic solvents, plasticizers and / or water, the copolymer mixture according to the invention mixed and the mixture thus obtained dispersed.
  • the solid concentrates prepared in various ways can then be divided into different substrates such. For example, alkyd resins, polyester resins, acrylate resins, polyurethane resins or epoxy resins may be incorporated.
  • pigments can also be dispersed directly in the copolymer mixtures according to the invention without solvent, and are then particularly suitable for pigmenting thermoplastic and thermoset plastic formulations.
  • novel copolymer blends can also be advantageously used in the production of color filters for liquid crystal displays, monitors, color resolution devices, sensors, plasma screens, displays based on the SED (Surface Conduction Electron Emitter Display) and for MLCC (Multi Layer Ceramic Compounds).
  • SED Surface Conduction Electron Emitter Display
  • MLCC Multi Layer Ceramic Compounds
  • the copolymer mixtures according to the invention can also be used for the preparation of cosmetic preparations such as, for example, make-ups, powders, lipsticks, hair dyes, creams, nail varnishes and sunscreen preparations. These may be in the usual forms, such as W / O or O / W emulsions, solutions, gels, creams, lotions or sprays.
  • the copolymer mixtures according to the invention can advantageously be used in dispersions used to prepare these preparations. These may contain the carrier media customary for these purposes in cosmetics, such as, for example, water, castor oils or silicone oils and solids, for example organic and inorganic pigments, such as titanium dioxide or iron oxide.
  • the invention also provides the use of such a dispersant for producing a pigmented coating on a substrate, wherein the pigmented paint is applied to the substrate and wherein the pigmented paint applied to the substrate is baked or cured or crosslinked.
  • copolymer blends may be used alone or in conjunction with conventional binders.
  • a use according to the invention of the copolymer mixtures also consists in the production of dispersible powder-particle and / or fibrous-particle-shaped solids, in particular of dispersible pigments or plastic fillers, the particles being coated with the copolymer mixture.
  • Such coatings of organic as well as inorganic solids are carried out in a known manner, as z.
  • the solvent or emulsifier can either be removed or remain in the mixture to form pastes.
  • These pastes are common commercial products and may additionally contain binder portions as well as other auxiliaries and additives.
  • the coating of the pigment surface can take place during or after the synthesis of the pigments, for example by adding the copolymer mixtures according to the invention to the pigment suspension or during or after the pigment finish.
  • the pretreated in this way pigments are characterized by easier incorporation and improved viscosity, flocculation and gloss behavior and higher color strength over untreated pigments from.
  • Suitable pigments are, for example, mono-, di-, tri- and polyazo-pigments, oxazine, dioxazine, thiazine pigments, diketo-pyrrolo-pyrroles, phthalocyanines, ultramarine and other metal complex pigments, indigoid pigments, diphenylmethane, triarylmethane, xanthan , Acridine, quinacridone, methine pigments, anthraquinone, pyranthrone, perylene and other polycyclic carbonyl pigments. Further examples of organic pigments can be found in the monograph: W. Herbst, K.
  • inorganic pigments are pigments based on Carbon black, graphite, zinc, titanium dioxide, zinc oxide, zinc sulfide, zinc phosphate, barium sulfate, lithophones, iron oxide, ultramarine, manganese phosphate, cobalt aluminate, cobalt stannate, cobalt zincate, antimony oxide, antimony sulfide, chromium oxide, zinc chromate, mixed metal oxides based on nickel, bismuth, vanadium, molybdenum , Cadmium, titanium, zinc, manganese, cobalt, iron, chromium, antimony, magnesium, aluminum (for example nickel titanium yellow, bismuth vanadate molybdate yellow or chrome titanium yellow), magnetic pigments based on pure iron, iron oxides and chromium oxides or mixed oxides, metallic effect pigments of aluminum, Zinc
  • nanoscale organic or inorganic solids having particle sizes below 100 nm, such as certain types of carbon black or particles consisting of a metal or semimetal oxide or hydroxide, as well as particles composed of mixed metal and / or semimetal oxides or hydroxides consist.
  • the oxides and / or oxide hydroxides of aluminum, silicon, zinc, titanium, and the like can be used to produce such extremely fine particulate solids.
  • the production process of these oxidic or hydroxidischen or oxidhydroxidischen particles can take place over the most different procedures such as ion exchange processes, plasma processes, sol-gel process, precipitation, comminution (for example by grinding) or flame hydrolysis and the like.
  • pulverulent or fibrous fillers are, for example, those which consist of pulverulent or fibrous particles of aluminum oxide, aluminum hydroxide, silicon dioxide, kieselguhr, silica, quartz, silica gel, talc, kaolin, mica, perlite, feldspar, shale meal, calcium sulfate, barium sulfate, Calcium carbonate, calcite, dolomite, glass or carbon are constructed.
  • pigments or fillers can be found, for example, in US Pat EP-A-0 270 126 .
  • flame retardants such as aluminum or magnesium hydroxide and matting agents such as silicas can also be dispersed and stabilized excellent.
  • the choice of the pigment affinic groups and the ethylenically unsaturated monomers depends on the pigment to be dispersed as well as the liquid medium and the binder and may vary from case to case.
  • the monomers may, for example, be chosen so that they interact with the material to be dispersed.
  • acid groups are frequently used as pigment-affine groups for basic pigment surfaces, and basic groups for acidic pigment surfaces or organic pigments.
  • wetting and dispersing agent is very often rendered water-soluble via the salt of an acidic group.
  • Another object of the present invention are paints, pastes and molding compositions containing the copolymer mixtures of the invention and one or more pigments, organic solvents and / or water, and optionally binder and customary auxiliaries. Furthermore, pigments coated with the novel copolymer blends are the subject of the invention.
  • Polymer 1 (Comparative Example, random copolymer A produced by free-radical polymerization)
  • 80 g of the polymer solution are reacted with 4.88 g of benzoic acid and 8.72 g of t-butylphenyl glycidyl ether at 120 ° C. for 2 h.
  • the polymer solution is adjusted with 1-methoxy-2-propyl acetate to a solids content of 50%.
  • Polymer 2 (diblock copolymer A made with NMP)
  • Polymer 3 (diblock copolymer A made with RAFT)
  • 150 g of the polymer solution are reacted with 12.5 g of benzoic acid and 22.3 g of t-butylphenyl glycidyl ether at 120 ° C. for 2 h.
  • the polymer solution is adjusted with 1-methoxy-2-propyl acetate to a solids content of 50%.
  • Polymer 4 (diblock copolymer B made with GTP)
  • Dispersion 40 min at 40 ° C and 8000 rpm, Dispermat CV
  • Epikote varnish Epikote 1001 (75% in Xylene) 60.0 Xylene 17.0 2-methoxy 12.8 n-butanol 10.0 BYK-325 0.2 100.0
  • Harder Versamid 115/70 71.0 Xylene 12.0 2-methoxy 8.0 n - butanol 9.0 100.0
  • Coating and curing of the paint pigment concentrate 2.6 paint 18.3 Harder 9.1 30.0
  • Synthalat paint Synthalat F 477/55% i.
  • the pigment concentrate is shaken with the paint for 5 minutes.
  • the mixture is homogenized once more after adding the hardener. After the application, a rub-out test is performed. Drying of the paint film at room temperature.
  • a bad finish is characterized by rating level 3 for flocculation tendency, visual rating or / and a ⁇ E value greater than 2 at rub-out.
  • the use of polymers 1 to 5 for each polymer leads, at least in one case, to disadvantageous properties such as high viscosity of the pigment concentrate or poor quality of the topcoats such as specks or flocculates.
  • the polymer blends of the invention M2, M3 and M5 compared to the prior art (the individual polymers and the polymer blends M1 and M4) for both pigments good Auflackrough in both selected binder systems. These results show the broader utility of the polymer blends of the invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (22)

  1. Composition comprenant deux copolymères linéaires structurés choisis dans le groupe consistant en copolymères séquencés et copolymères à gradient, caractérisée en ce que lesdits copolymères sont produits avec des techniques de polymérisation contrôlée différents et la différence des polydispersités desdits copolymères Δ(Mw/Mn) ≥ 0,25.
  2. Composition selon la revendication 1, la composition comprenant deux copolymères séquencés linéaires qui sont produits avec des techniques de polymérisation contrôlée différents et la différence des polydispersités des deux copolymères séquencés Δ(Mw/Mn) ≥ 0,25.
  3. Composition selon la revendication 1, la composition comprenant deux copolymères à gradient linéaires qui sont produits avec des techniques de polymérisation contrôlée différents et la différence des polydispersités des deux copolymères à gradients Δ(Mw/Mn) ≥ 0,25.
  4. Composition selon la revendication 1, la composition comprenant un copolymère séquencé linéaire et un copolymère à gradient linéaire, les copolymères étant produits avec des techniques de polymérisation contrôlée différents et la différence des polydispersités des deux copolymères Δ(Mw/Mn) ≥ 0,25.
  5. Composition selon l'une quelconque des revendications 1, 2 ou 4, un ou plusieurs des copolymères séquencés étant des copolymères séquencés AB, ABA ou ABC.
  6. Composition selon la revendication 2, un copolymère séquencé étant un copolymère séquencé AB et l'autre copolymère séquencé étant un copolymère séquencé AB, ABA ou ABC.
  7. Composition selon une ou plusieurs des revendications 1, 2 ou 4 à 6, au moins un des blocs dudit copolymère séquencé étant composé d'au moins deux monomères monopolymérisés éthyléniquement non-saturés différents.
  8. Composition selon la revendication 7, tous les blocs dans un copolymère séquencé étant respectivement composés d'au moins deux monomères monopolymérisés éthyléniquement non-saturés différents.
  9. Composition selon une ou plusieurs des revendications 1 à 8, les deux copolymères linéaires structurés étant présents dans une proportion pondérale de l'un par rapport à l'autre de 5 : 95 à 95 : 5.
  10. Composition selon une ou plusieurs des revendications 1 à 9, la polydispersité des copolymères respectivement possédant une valeur de 1,05 à 4.
  11. Composition selon une ou plusieurs des revendications 1 à 10, la masse molaire moyenne en nombre des copolymères respectivement étant de 1000 à 20000 g/mol.
  12. Composition selon une ou plusieurs des revendications 1 à 11, les techniques de polymérisation contrôlée étant choisis dans le groupe consistant en RAFT, NMP, ATRP, GTP, la polymérisation radicalaire contrôlée avec tétraphényléthane, la polymérisation radicalaire contrôlée avec 1,1-diphényléthène, la polymérisation radicalaire contrôlée avec des iniferters et la polymérisation radicalaire contrôlée avec des complexes organiques de cobalt.
  13. Composition selon une ou plusieurs des revendications 1 à 12, la composition étant une agent mouillant et de dispersion.
  14. Composition selon la revendication 13, la composition contenant 10 % au maximum d'un ou plusieurs copolymères statistiques ou homopolymères.
  15. Composition selon la revendication 14, qui est essentiellement exempte des copolymères statistiques et homopolymères.
  16. Procédé pour la fabrication des compositions selon une ou plusieurs des revendications 1 à 15, lesdits copolymères étant mélangés sous forme de solution, le cas échéant avec chauffage.
  17. Utilisation d'une composition selon une ou plusieurs des revendications 1 à 15 ou obtenue selon le procédé de la revendication 16 en tant qu'agent mouillant et/ou agent de dispersion.
  18. Utilisation selon la revendication 17, l'agent mouillant et/ou l'agent de dispersion étant utilisé dans la fabrication des vernis, encres, couchage du papier, teintures de cuir et textiles, pâtes, concentrés de pigments, céramiques, préparations cosmétiques, masses de coulée ou masses de moulage, filtres colorés pour affichages à cristaux liquide, écrans à cristaux liquide, dispositifs de résolution des couleurs, capteurs, écrans à plasma, affichages à base de SED et pour MLCC.
  19. Utilisation selon la revendication 17, l'agent mouillant et/ou l'agent de dispersion étant utilisé pour le revêtement des pigments ou matériaux de remplissage.
  20. Utilisation selon la revendication 19, lesdits pigments ou matériaux de remplissage possédant une dimension de particule au-dessous 100 nm.
  21. Vernis, pâtes, masses de coulée et masses de moulage contenant une composition selon une ou plusieurs des revendications 1 à 15 ou obtenue selon le procédé de la revendication 16.
  22. Pigments ou matériaux de remplissage revêtus avec une composition selon une ou plusieurs des revendications 1 à 15, ou obtenue selon le procédé de la revendication 16.
EP07818854.7A 2006-10-10 2007-10-09 Agents mouillants et agents dispersants à base de mélanges de copolymères structurés Not-in-force EP2091984B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006048144A DE102006048144A1 (de) 2006-10-10 2006-10-10 Netz- und Dispergiermittel basierend auf Mischungen von strukturierten Copolymeren
PCT/EP2007/008781 WO2008043529A2 (fr) 2006-10-10 2007-10-09 Agents mouillants et agents dispersants à base de mélanges de copolymères structurés

Publications (2)

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EP2091984A2 EP2091984A2 (fr) 2009-08-26
EP2091984B1 true EP2091984B1 (fr) 2013-06-05

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US (1) US8871856B2 (fr)
EP (1) EP2091984B1 (fr)
JP (1) JP5145345B2 (fr)
KR (1) KR101247360B1 (fr)
CN (1) CN101535358A (fr)
DE (1) DE102006048144A1 (fr)
TW (1) TW200833767A (fr)
WO (1) WO2008043529A2 (fr)

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CN103180354B (zh) * 2010-11-08 2015-02-25 日本曹达株式会社 新型共聚物
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US8871856B2 (en) 2014-10-28
JP2010506016A (ja) 2010-02-25
DE102006048144A1 (de) 2008-04-17
JP5145345B2 (ja) 2013-02-13
TW200833767A (en) 2008-08-16
US20100168316A1 (en) 2010-07-01
WO2008043529A2 (fr) 2008-04-17
EP2091984A2 (fr) 2009-08-26
CN101535358A (zh) 2009-09-16
KR20090078821A (ko) 2009-07-20
WO2008043529A3 (fr) 2009-05-22
KR101247360B1 (ko) 2013-03-26

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